CN104091927B - WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes and preparation method - Google Patents
WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes and preparation method Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of WS2-Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes and preparation method thereof, its electrochemistry storage magnesium active material is WS2-The composite nano materials of nanometer sheet/Graphene with holes, WS in composite nano materials2The ratio of the amount of substance of nanometer sheet with holes and Graphene is 1:1-1:3, WS2Nanometer sheet with holes is few number of plies, and the component of combination electrode and mass percentage content thereof are: WS2Nanometer sheet/Graphene composite nano materials with holes is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%. Preparation process: first prepare WS2Nanometer sheet/Graphene composite nano materials with holes, by prepared composite nano materials and acetylene black, carboxymethyl cellulose and Kynoar furnishing slurry, is coated onto on collector, and dry rear roll extrusion obtains. Composite nano materials electrochemistry storage magnesium combination electrode prepared by the present invention has high reversible storage magnesium capacity, is with a wide range of applications.
Description
Technical field
The present invention relates to electrochemistry storage magnesium combination electrode and preparation method thereof, relate in particular to WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes and preparation method thereof, belongs to new energy materials, energy storage and switch technology field.
Background technology
Along with the development of modern mobile communication, new-energy automobile and intelligent grid, novel electrochmical power source has played more and more important effect in modern society. Traditional secondary cell, if lead-acid accumulator is because it is containing harmful metallic element Pb, its application is restricted. Lithium ion battery has the excellent properties such as high specific energy, memory-less effect, environmental friendliness, in the Portable movable such as mobile phone and notebook computer electrical equipment, is widely used. As electrokinetic cell, lithium ion battery is also with a wide range of applications at aspects such as electric bicycle, electric automobile and intelligent grids. But due to never solution carefully and lithium resource limited of the security of lithium ion battery, lithium ion battery still also exists a lot of work to do as the extensive use of electrokinetic cell and storage battery. Along with the development of new-energy automobile and the large-scale application of storage battery substitute the secondary cell of a kind of cheapness, environmental friendliness and the height ratio capacity of existing secondary cell system in the urgent need to finding a kind of energy. Because divalence magnesium ion has less radius, can electrochemical intercalation and deintercalation in the compound of some layer of structure, as inorganic transition metal oxide, sulfide etc. Magnesium also has aboundresources in addition, cheap, specific energy is high, nontoxic and process the advantages such as convenient. Therefore, rechargeable magnesium ion battery also becomes the research system of a new secondary cell in recent years. But up to the present still little as the electrode material of high performance electrochemistry storage magnesium.
WS2Having and layer structure like graphite-like, is the S-W-S of covalent bonds in its layer, is weak Van der Waals force between layers. WS2Weak interlaminar action power and larger interlamellar spacing allow to be reacted at its interlayer and introduced external atom or molecule by insertion. Such characteristic makes WS2Material can be used as the material of main part that inserts reaction. Therefore, WS2It is a kind of electrode material of rising electrochemistry storage magnesium. But general WS2Nano material electrochemistry storage magnesium performance can't meet practical application, and its electrochemistry storage magnesium capacity is lower, only has 50-60mAh/g.
Two-dimensional nano material has the characteristic of numerous excellences with its unique pattern, its research has caused people's very big interest. Graphene is most typical two-dimensional nano material, and its unique two-dimensional nano chip architecture makes the performances such as physics, chemistry and the mechanics of its numerous uniquenesses, has important scientific research meaning and technology application prospect widely. Graphene has high specific area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics make Graphene be with a wide range of applications in nano electron device, the novel field such as catalyst material and electrochemistry energy storage and energy conversion.
The immense success that the discovery of Graphene and research thereof obtain has excited the very big interest of people to other inorganic two-dimensional nano investigations of materials, as the transition metal dichalcogenide of individual layer or few number of plies etc. Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, namely for the inorganic material of layer structure, in the time that its number of plies reduces (below approximately 6 layers), especially reduce 4 layers and when following, its electronic property or band structure can produce obvious variation, thereby cause it to show the physics and chemistry characteristic different from corresponding body phase material. Except Graphene, as body phase WS2Reduce to few number of plies when individual layer (particularly), shown and the visibly different physics of body phase material, chemical characteristic. Research shows the WS of individual layer or few number of plies2Nanometer sheet has better electrochemistry storage magnesium performance. But as the electrode material of electrochemistry storage magnesium, WS2Low electric conductivity between layers affected the performance of its application.
Due to WS2Nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, and both have good similitude on microscopic appearance and crystal structure. If by WS2The composite of nanometer sheet and the compound preparation of Graphene, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite, strengthen the electronics transmission in electrochemistry storage magnesium electrode course of reaction, can further improve the electrochemistry storage magnesium performance of composite. With common WS2Nanometer sheet comparison, the WS of little nano-sheet pattern with holes2Not only there is more edge, more short magnesium ion diffusion admittance can be provided, and load on Graphene, there is more contact area with electrolyte. Therefore WS2The composite nano materials of nanometer sheet/Graphene with holes can show the electrochemistry storage magnesium performance of remarkable enhancing.
But, up to the present, use WS2Nanometer sheet/Graphene composite nano materials with holes have not been reported as electrochemistry storage magnesium combination electrode and the preparation thereof of electroactive substance. First the present invention is raw material with graphene oxide and sulfo-ammonium tungstate, and the hydrothermal method of assisting by cationic post [5] aromatic hydrocarbons and heat treatment subsequently, prepared WS2The composite nano materials of nanometer sheet/Graphene with holes, then uses WS2The composite nano materials of nanometer sheet/Graphene with holes, as the active material of electrochemistry storage magnesium, has been prepared the combination electrode of electrochemistry storage magnesium. The present invention prepares WS2The method of nanometer sheet/graphene nano material electrochemical storage magnesium combination electrode with holes has simply, facilitates and be easy to expand industrial applications a little.
Summary of the invention
The object of the present invention is to provide a kind of WS2-Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes and preparation method thereof, the electrochemistry storage magnesium active material of described combination electrode is WS2-The composite nano materials of nanometer sheet/Graphene with holes, WS in described composite nano materials2The ratio of the amount of substance of nanometer sheet with holes and Graphene is 1:2, described WS2Nanometer sheet with holes is the layer structure of individual layer or few number of plies, and the component of described combination electrode and mass percentage content thereof are: WS2Nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
The layer structure of few number of plies refers to the layer structure of the number of plies below 6 layers or 6 layers.
WS of the present invention2-The preparation method of nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes comprises the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add the two ammonium bromides (its structure is shown in Fig. 1) of cationic post [5] aromatic hydrocarbons N-dodecyl trimethylene diamine, and fully stir, then add successively Cys and sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, the ratio of the amount of substance of Cys and sulfo-ammonium tungstate consumption is 5:1, sulfo-ammonium tungstate with the ratio of the amount of substance of graphene oxide at 1:1-1:3;
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, the molar concentration of cationic post [5] aromatic hydrocarbons is 0.0015mol/L, the molar concentration of graphene oxide is 30-65mmol/L, this reactor is put in constant temperature oven, at 230-250 DEG C after hydro-thermal reaction 24h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal reaction solid product, and fully wash by deionized water, vacuum drying at 100 DEG C, by the hydro-thermal solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, hydrogen volume mark is 10%, finally prepare WS2The composite nano materials of nanometer sheet/Graphene with holes;
(3) by the WS of above-mentioned preparation2Nanometer sheet/Graphene composite nano materials with holes is as the electrochemistry storage magnesium active material of preparing combination electrode, under agitation fully mix the uniform slurry of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, each constituent mass percentage is: WS2Nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, is coated onto this slurry on the foam copper of collector equably, vacuum drying at 110 DEG C, roll extrusion obtains WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
WS of the present invention2Nanometer sheet/Graphene electrochemistry with holes storage magnesium combination electrode and preparation method thereof has the following advantages: graphene oxide surface and edge with a lot of oxygen-containing functional groups (as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups are more easily dispersed in water or organic liquid graphene oxide, but these oxygen-containing functional groups make graphene oxide surface with negative electrical charge, make graphene oxide and the WS with negative electrical charge4 2-The mutual Coulomb repulsion of ion, the present invention is first adsorbed onto graphene oxide surface by cationic post [5] aromatic hydrocarbons by electrostatic interaction, makes it with part positive charge, due to electrostatic interaction, WS4 2-Ion is just easy to interact and combine with the graphene oxide that has adsorbed cationic post [5] aromatic hydrocarbons. The more important thing is, compared with common ionic surface active agent, respectively there is the quaternary ammonium hydrophilic radical of 5 positively chargeds at the two ends of cationic post [5] arene-based supermolecule that the present invention uses, and between electronegative graphene oxide, have stronger mutual electrostatic interaction; This cationic post [5] arene-based supermolecule can be adsorbed on graphene oxide surface in mode vertical or that lie low, and be entrained to together in hydrothermal product in hydrothermal treatment consists process, in heat treatment process, cationic post [5] arene-based supermolecule is carbonized, and finally can prepare with being permitted microporous WS2The composite nano materials of nanometer sheet and Graphene. This WS2Nanometer sheet with holes has more edge, as electrochemistry storage magnesium material, can provide the diffusion admittance of more short magnesium ion, contributes to strengthen its electrochemistry storage magnesium performance; In addition, WS2Nanometer sheet/graphene composite material with holes can increase the contact area of itself and electrolyte, can further contribute to improve its chemical property. Therefore, the present invention WS2The electrochemistry storage magnesium electrode that nanometer sheet/graphene composite material with holes is prepared as electroactive substance has high electrochemistry storage magnesium capacity, excellent cycle performance and the remarkable large current density electrical characteristics that strengthen.
Brief description of the drawings
The cationic post of Fig. 1 [5] aromatic hydrocarbons structural representation.
The WS that Fig. 2 embodiment 1 prepares2The XRD figure of nanometer sheet/Graphene composite nano materials with holes.
The WS that Fig. 3 embodiment 1 prepares2The SEM shape appearance figure (a) of nanometer sheet/Graphene composite nano materials with holes and transmission electron microscope photo (b).
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: 0oUnder C ice bath, 10.0mmol (0.12g) graphite powder dispersed with stirring, in the 50mL concentrated sulfuric acid, is slowly added to KMnO under constantly stirring4, institute adds KMnO4Quality be 4 times of graphite powder, stir 50 minutes, in the time of temperature rise to 35 DEG C, slowly add 50mL deionized water, then stir 30 minutes, add the H of 15mL mass fraction 30%2O2, stir 30 minutes, through centrifugation, after HCl solution, deionized water and the acetone cyclic washing with mass fraction 5%, obtain graphene oxide successively.
Embodiment 1.
1) be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, add again the cationic post of 0.12mmol [5] aromatic hydrocarbons, and fully stir, then add successively 0.76g (6.25mmol) Cys and 1.25mmol sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely about 80mL of deionized water adjustment volume;
2) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash by deionized water, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares WS2The composite nano materials of nanometer sheet/Graphene with holes, WS in composite nano materials2With the ratio of Graphene amount of substance be 1:2, with XRD, SEM and TEM are to the prepared WS that obtains2The composite nano materials of nanometer sheet/Graphene with holes characterizes (seeing Fig. 2 and Fig. 3), and result shows to load in composite nano materials the WS on Graphene2Be with being permitted lacunary nanometer sheet, its number of plies is at layer 2-4, and the average number of plies is 3 layers;
3) by the WS of above-mentioned preparation2Nanometer sheet/Graphene composite nano materials with holes is as the electrode active material of electrochemistry storage magnesium, under agitation fully mix the uniform slurry of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, this slurry is coated onto on the foam copper of collector (foam copper porosity is greater than 90%) equably, vacuum drying at 110 DEG C, then roll extrusion obtains WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes, in combination electrode, each constituent mass percentage is: WS2Nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
The performance test of electrochemistry storage magnesium: taking combination electrode as working electrode, with metal magnesium sheet as to electrode, the Mg[AlCl that electrolyte is 0.25mol/L2(C4H9)(C2H5)]2Tetrahydrofuran solution be electrolyte, porous polypropylene film (Celguard-2300) is barrier film, in the suitcase that is full of argon gas, is assembled into test battery. By the electrochemistry storage magnesium performance of constant current charge-discharge test compound electrode, charge and discharge cycles is carried out on programme controlled auto charge and discharge instrument, charging and discharging currents density 50mA/g, voltage range 0.3 ~ 3.0V. Electrochemical results shows: WS2The initial reversible capacity of electrochemistry storage magnesium of nanometer sheet/graphene combination electrode with holes is 283mAh/g, and after 50 circulations, reversible capacity is 272mAh/g, has shown high specific capacity and excellent stable circulation performance; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its capacity is 237mAh/g, has shown its high power charging-discharging characteristic (with comparative example comparison below) significantly strengthening.
Comparative example
Adopt DTAB cationic surfactant, prepared WS by above-mentioned similar approach2Nanometer sheet/Graphene electrochemistry storage magnesium nano material combination electrode, concrete preparation process is as follows:
Be dispersed in 60mL deionized water ultrasonic 2.5mmol graphene oxide, add again 1.2mmol DTAB cationic surfactant, and fully stir, then add successively 0.76g (6.25mmol) Cys and 1.25mmol sulfo-ammonium tungstate, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely about 80mL of deionized water adjustment volume, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash by deionized water, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepare WS2The nano composite material of nanometer sheet/Graphene, WS in composite nano materials2With the ratio of the amount of substance of Graphene be 1:2. With XRD, SEM and TEM are to finally preparing WS2The nano composite material of nanometer sheet/Graphene characterizes, and result shows WS in composite nano materials2For layer structure, the average number of plies is 7 layers, loads on the WS on Graphene2For nanometer sheet, do not find significantly sky, WS2The number of plies of nanometer sheet is mainly at 6-9 layer, and the average number of plies is 7 layers.
With prepared WS2Nanometer sheet/Graphene composite nano materials is electrochemistry storage magnesium active material, by above-mentioned steps 3) process prepare WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode, and test its electrochemistry storage magnesium performance by aforementioned identical electrochemical test method. Result shows: WS2The initial reversible capacity of nanometer sheet/Graphene electrochemistry storage magnesium combination electrode electrochemistry storage magnesium is that 186mAh/g(charging and discharging currents is 50mA/g), after 50 circulations, reversible capacity is 162mAh/g; In the time of high current charge-discharge (charging and discharging currents is 800mA/g), its capacity is 102mAh/g.
Claims (2)
1. a WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes, is characterized in that the electrochemistry storage of described combination electrodeMagnesium active material is WS2The composite nano materials of nanometer sheet/Graphene with holes, WS in described composite nano materials2Nanometer with holesThe ratio of the amount of substance of sheet and Graphene is (1:1)-(1:3), described WS2Nanometer sheet with holes is the layer structure of few number of plies, described fewThe layer structure of the number of plies refers to the layer structure of the number of plies below 6 layers, the component of described combination electrode and mass percentage content thereofFor: WS2Nanometer sheet/Graphene composite nano materials 80% with holes, acetylene black 10%, carboxymethyl cellulose 5%, polyvinylidene fluorideAlkene 5%, the preparation method of described combination electrode comprises the following steps:
(1) be dispersed in deionized water ultrasonic graphene oxide, add cationic post [5] aromatic hydrocarbons, and fully stir, then comply withInferior Cys and the sulfo-ammonium tungstate of adding, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, L-half GuangThe ratio of the amount of substance of propylhomoserin and sulfo-ammonium tungstate consumption is 5:1, and sulfo-ammonium tungstate exists with the ratio of the amount of substance of graphene oxide1:1-1:3；
(2) mixed dispersion step (1) being obtained is transferred in hydrothermal reaction kettle, and adds deionized water to adjust volume to water80% of thermal response still nominal volume, the molar concentration of cationic post [5] aromatic hydrocarbons is 0.0015mol/L, the rubbing of graphene oxideYour concentration is 30-65mmol/L, and this reactor is put in constant temperature oven, at 230-250 DEG C, after hydro-thermal reaction 24h, allows itNaturally cool to room temperature, collect hydro-thermal reaction solid product with centrifugation, and fully wash by deionized water, at 100 DEG CVacuum drying, by the hydro-thermal reaction solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, mixIn atmosphere, hydrogen volume mark is 10%, finally prepares WS2The composite nano materials of nanometer sheet/Graphene with holes;
(3) by the WS of above-mentioned preparation2Nanometer sheet/Graphene composite nano materials with holes is lived as the electrochemistry storage magnesium of preparing combination electrodeProperty material, is stirring with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%Mix the uniform slurry of lower abundant mixing furnishing, this slurry is coated onto equably on the foam copper of collector, true at 110 DEG CEmpty dry, roll extrusion obtains WS2Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes;
The structural formula of described cationic post [5] aromatic hydrocarbons is:
2. WS according to claim 12Nanometer sheet/Graphene electrochemistry storage magnesium combination electrode with holes, is characterized in that described WS2The number of plies of nanometer sheet with holes is 2～4 layers.
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